Dyeing of in Particular Human Keratin Materials by Dry Thermal Transfer of a Direct Dye, Composition Comprising the Said Dye and Its Method of Preparation

ABSTRACT

The subject of the present invention is the use, for dyeing in particular human keratin materials, of a direct dye, in particular an azo dye, by dry thermal transfer. Its subject is furthermore a method for dyeing keratin materials, n which at least one direct dye, in particular one azo dye, contained in a dry composition, is applied to or close to the keratin materials, and a source of heat is applied, causing the thermal transfer of the direct dye(s) at the surface and/or inside the keratin materials. It relates furthermore to the dry composition and a method for preparing it.

The subject of the present invention is the use, for dyeing inparticular human keratin materials, of a direct dye by dry thermaltransfer. Its subject is furthermore a method for dyeing keratinmaterials in which a dry solid composition comprising the said directdye is used. It relates furthermore to the composition and its method ofpreparation.

The invention relates more particularly to the field of dyeing humankeratin fibres, and in particular hair.

It has been known for a long time to modify the colour of hair, and inparticular to mask grey hair.

Essentially two types of technology are known which are used to dyehuman keratin fibres.

The first method, called direct or semipermanent dyeing, consists inchanging or providing colour by the application of a coloured moleculewhich penetrates by diffusion into the fibre and/or remains adsorbed atits surface.

The second method, called oxidation dyeing or permanent dyeing, consistsin changing or providing colour using, on the very inside of the fibre,an oxidative condensation of dye precursors which are weakly coloured orcolourless compounds. After this reaction, the dyes formed are insolubleand are trapped inside the fibre.

The two methods summarized above make it possible to obtain numerouscolours.

On the other hand, these methods are used with liquid compositions,which has the consequence of making these methods “messy” for clothes,hairdressing accessories (combs, towels and the like), tubs and thelike.

Moreover, the dyeing times are generally long because the time forrinsing the product and the time for drying the hair should be added tothe leave-in time for the composition.

Finally, the use of some dyes offering good dyeing performance on thefibres is sometimes limited because of their low solubility in liquidformulation carriers.

As can be seen, there is a constant search for methods for dyeing humankeratin materials which, while allowing effective dyeing to be obtained,do not have the disadvantages mentioned above.

The subject of the present invention is therefore a method for dyeingkeratin materials which make it possible to rapidly dye hair usingthermal transfer of dyes, and in particular of specific azo dyes.

This method has the advantage of not requiring the use of a liquidformulation carrier for the dye, which makes the dyeing particularlyscarcely messy.

Furthermore, the fact that a liquid carrier is not required and that thedyes are used in a solid form makes it possible to use dyes which aresparingly soluble or which are unstable in conventional dyeing media.This can contribute to further broadening the pallet of colourspossible.

Moreover, still by virtue of the fact that the dye is initially used ina solid form, there is no need either for rinsing, or for shampooingand/or for drying the materials treated.

Furthermore, thermal transfer being rapid, the leave-in times are short.

The latter two factors contribute to making the method according to theinvention more rapid than conventional methods.

Finally, this method makes it possible to produce, in a simple manner,motifs on the materials treated, in particular on the hair.

Thus, the first subject of the present invention is the use of at leastone direct dye for dyeing in particular human keratin materials by drythermal transfer.

Its subject is likewise a method for dyeing in particular human keratinmaterials, in which at least one direct dye contained in a drycomposition is applied to or close to the keratin materials, and asource of heat is applied, causing the thermal transfer of the directdye(s) at the surface and/or inside the keratin materials.

Its subject is furthermore a dry composition, in the form of a dividedor undivided solid, comprising at least one direct dye and at least onefilm-forming polymer.

Finally, its subject is a method for preparing this composition, inwhich a mixture comprising at least one direct azo dye, at least onefilm-forming polymer and at least one solvent are applied to a support,and then the said solvent is evaporated.

However, other characteristics and advantages of the present inventionwill emerge more clearly on reading the description and the exampleswhich follow.

In the text which follows, when it is specified that the composition is“dry”, that means that the variation in the dry extract of such acomposition, measured before and after a thermal treatment in an ovenfor one hour at 100° C., varies by 20% by weight or less, preferably by10% by weight or less.

It is recalled that a solid compound is a compound which does not flowor does not undergo deformation when it is subjected to moderate forces.It should be noted that when the compound is in the form of a dividedsolid, the characteristics which have just been recalled apply at thelevel of the particle and not of a combination of particles deposited orotherwise on a support.

Moreover, the expression thermal transfer is understood to mean, for thepurposes of the present invention, the application of heat to the drycomposition brought into contact with the keratin materials to betreated or close to them. This heat is obtained by means of a source ata temperature more particularly between 100 and 500° C., advantageouslybetween 130 and 250° C. and preferably between 140 and 220° C.

Preferably, this source of heat is brought into contact with the wholeof the dry composition and keratin materials to be treated.

Without being bound by any theory, one of the possible mechanisms fordyeing keratin materials involves a step of vaporization or sublimationof the direct dye present in the dry composition according to theinvention.

Human keratin materials denote more generally keratin fibres, such ashair or the eyelashes.

It should finally be recalled that, unless otherwise stated, the limitsdelimiting a range of values form part of this range.

As indicated above, this method according to the invention is carriedout using at least one direct dye.

Suitable are the direct dyes customarily used in the field for dyeingkeratin fibres. These dyes may be non-ionic, cationic or anionic.

By way of examples of suitable dyes, there may be mentioned theacridine, acridone, anthranthrone, anthrapyrimidine, anthraquinone,azine, azo, azomethine, benzanthrone, benzimidazole, benzimidazolone,benzindole, benzoxazole, benzopyran, benzothiazole, benzoquinone,bisazine, bisisodinoline, carboxanilide, coumarin, cyanine (such as forexample azacarbocyanine, diazacarbocyanine, diazahemicyanine,hemicyanine, tetraazacarbocyanine), diazine, diketopyrrolopyrrole,dioxazine, diphenylamine, diphenylmethane, dithiazine, flavonoid such asflavanthrone and flavone, fluoroindine, formazan, hydrazone inparticular arylhydrazone, hydroxyketone, indamine, indanthrone,indigoid, and pseudo-indigoid, indophenol, indoaniline, isoindoline,isoindolinone, isoviolanthrone, lactone, methine, naphthalimide,naphthanilide, naphtholactam, naphthoquinone, nitro(hetero)aromatic,oxadiazole, oxazine, perilone, perinone, perylene, phenazine,phenothiazine, phthalocyanine, polyene/carotenoid, porphyrine,pyranthrone, pyrazoloanthrone, pyrazolone, pyrimidinoanthrone, pyronine,quinacridone, quinoline, quinophthalone, squarane, stilbene,tetrazolium, thiazine, thioindigo, thiopyronine, triarylmethane andxanthene dyes, alone or as mixtures.

According to a particularly advantageous embodiment of the invention,the direct dye is chosen from azo dyes.

Preferably, the azo dye corresponds to the following formula (I):

in which:n and n′, which are identical or different, represent an integer between1 and 5 inclusive,R, which are identical or not, R′, which are identical or not,independently of each other, represent

-   -   a hydrogen atom;    -   a linear, branched or cyclic, saturated, unsaturated or        aromatic, C₁-C₃₀ hydrocarbon chain,        -   optionally substituted with one or more halogen atoms; with            one or more groups, which are identical or not, chosen from            the groups hydroxyl; nitro; cyano; carboxylic acid; allyl;            haloallyl; C₁-C₁₀ alkoxy; (C₁-C₄) alkylcarbonyl-amino;            (C₁-C₄) alkylaminocarbonyl; hydrogenocarbonylamino; (C₁-C₄)            alkylsulphonylamino; (C₁-C₄) alkoxycarbonylamino; (C₁-C₄)            alkoxycarbonyl; (C₁-C₄) alkylcarbonyl(C₁-C₄) alkoxycarbonyl;            CF₃; amino; amino optionally substituted with one or more            radicals which are identical or different, C₁-C₁₀ alkyl,            C₁-C₁₀ hydroxyalkyl, alkoxy-(C₁-C₁₀)alkyl, C₁-C₁₀            aminoalkyl, (C₁-C₁₀) (di)alkyl-amino(C₁-C₁₀)alkyl, C₁-C₁₀            cyanoalkyl, C₆-C₃₀ aryl, (C₆-C₃₀)aryl(C₁-C₄)alkyl,            (C₄-C₃₀)cyclo-(C₁-C₁₂)alkyl, (C₁-C₄)alkylcarbonyl,            (C₁-C₄)alkylcarboxy (C₁-C₄)alkyl, allyl, haloallyl;        -   optionally interrupted or attached to the aromatic ring via            one or more heteroatoms and/or groups comprising one or more            heteroatoms chosen from oxygen, sulphur, nitrogen;    -   a group hydroxyl; C₁-C₄ alkoxy; carboxylic acid; amino; amino        substituted with one or more radicals, which are identical or        different, chosen from the radicals C₁-C₄ alkyl, C₂-C₄ alkenyl,        C₁-C₄ cyanoalkyl, C₁-C₄ hydroxyalkyl, C₆-C₃₀ aryl,        (C₆-C₃₀)aryl(C₁-C₄)alkyl, allyl, (C₁-C₄)alkoxy(C₁-C₄)alkyl,        (C₄-C₃₀)cyclo(C₁-C₁₂)-alkyl, (C₁-C₄)alkylcarbonyl,        (C₁-C₄)alkylcarboxy (C₁-C₄)alkyl, haloallyl, (C₁-C₄)aminoalkyl,        (C₁-C₄)(di)alkylamino(C₁-C₄)alkyl, (C₁-C₄)-alkylsulphonyl,        (C₁-C₄)alkoxycarbonyl; halogen; allyl; hydrogenocarbonyl;        trifluoromethyl; nitro; cyano;        it being understood that at least one of the radicals R or R′        represents a group hydroxyl; nitro; cyano; amino; amino        optionally substituted with one or more radicals; and        optionally two radicals R carried by two adjacent carbon atoms        or two radicals R′ carried by two adjacent carbon atoms may form        with the aromatic ring carrying the carbon atoms to which each        is attached a fused ring of the naphthalene type optionally        substituted with an aminosulphonyl or (C₁-C₄)alkylaminosulphonyl        group.

Preferably, the direct azo dye corresponds to the following formula(Ia):

in which:

-   -   R′₁ represents a hydrogen atom, an amino group or a hydroxyl        group;    -   R′₂ represents a hydrogen atom, a halogen atom, a carboxylic        acid group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, an allyl        group or a C₁-C₄ aminocarbonylalkyl group;    -   R′₃ represents a hydrogen atom, a hydroxyl group or a group of        the NR′₁R′₂ type where R′₁ and R′₂ represent, independently of        each other, a hydrogen atom, a C₁-C₄ alkyl group, a C₂-C₄        alkenyl group, a C₁-C₄ cyanoalkyl group, a C₁-C₄ hydroxyalkyl        group, a C₆-C₃₀ aryl group, a (C₆-C₃₀)aryl(C₁-C₄)alkyl group, an        allyl group, a (C₁-C₄)alkoxy(C₁-C₄)alkyl group, a        (C₄-C₃₀)cyclo(C₁-C₁₂)alkyl group, a (C₁-C₄)alkyl-carbonyl group,        a (C₁-C₄)alkylcarboxy(C₁-C₄)alkyl group or a haloallyl group, a        C₁-C₄ aminoalkyl group, a (C₁-C₄)(di)alkylamino(C₁-C₄)alkyl        group;    -   R′₂ and R′₃ may form, with the benzene ring, a fused ring of the        naphthalene type optionally substituted with a group —SO₂—NHR        where R represents a hydrogen atom or an optionally substituted        C₁-C₄ alkyl chain;    -   R′₄ represents a hydrogen atom, a halogen atom, a hydroxyl        group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a        (C₁-C₄)alkoxy(C₁-C₄)alkyl group;    -   R′₅ represents a hydrogen atom, a halogen atom, a hydroxyl        group, an amino group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy        group, a (C₁-C₄)alkylcarbonylamino group, a        hydrogenocarbonylamino group, a (C₁-C₄)alkylsulphonylamino        group, a (C₁-C₄)alkoxycarbonylamino group or a CF₃ group;    -   R′₄ and R′₅ may form, with the benzene ring, a fused ring of the        naphthalene type;    -   R₁ represents a hydrogen atom, a halogen atom, a hydroxyl group,        a nitro group or a cyano group;    -   R₂ represents a hydrogen atom, a nitro group or a C₁-C₄ alkyl        group;

R₃ represents a hydrogen atom, a C₁-C₄ alkyl group, a C₁-C₄ alkoxygroup, a (C₄-C₃₀)cyclo(C₁-C₁₂)alkyl group, a C₂-C₄ alkenyl group, aC₁-C₄ alkoxycarbonyl group, a (C₁-C₄)alkylcarbonyl group, a(C₁-C₄)alkoxycarbonyl(C₁-C₄)alkoxycarbonyl group, a(C₁-C₄)alkylcarbonyl(C₁-C₄)alkoxycarbonyl group, an aryl group, an aminogroup, a nitro group, a cyano group or a CF₃ group;

-   -   R₄ represents a hydrogen atom or a nitro group;    -   R₅ represents a hydrogen atom, a halogen atom, a carboxylic acid        group, a hydroxyl group, an amino group, a cyano group or a        C₁-C₄ alkyl group;        it being understood that at least one of the radicals R′₁ to R′₅        and R₁ to R₅ represents a group hydroxyl; nitro; cyano; amino;        amino optionally substituted with one or more radicals.

According to an advantageous embodiment, the radicals R′₁, R′₂, R₁, R₂,R₄ represent a hydrogen atom.

More particularly, the radical R′₃ represents a hydrogen atom, a groupof the NR″₁R″₂ type where R″₁ and R″₂ represent, independently of eachother, a hydrogen atom, a C₁-C₄ alkyl group, a C₁-C₄ cyanoalkyl group, aC₁-C₄ hydroxyalkyl group, a C₁-C₄ aminoalkyl group.

As regards the radical R′₄, it represents more particularly a hydrogenatom.

Preferably, the radical R′₅ represents a hydrogen atom, a C₁-C₄ alkylgroup.

According to another embodiment, the radicals R′₄ and R′₅ form, with thebenzene ring, a fused ring of the naphthalene type.

The radical R₃ represents more particularly an amino group, a nitrogroup.

The radical R₅ represents more particularly a hydrogen atom; a halogenatom, preferably chlorine, fluorine; an amino group.

Preferably, the direct dye used in the context of the present invention,and advantageously the direct azo dye, is chosen from compounds havingan enthalpy of vaporization of less than or equal to 200 kJ/mol.

In accordance with an advantageous embodiment of the invention, thedirect azo dye is chosen from the following direct dyes: Solvent Brown 1[6416-57-5], Solvent Orange 1 [2051-85-6], Solvent Orange 7 [3118-97-6],Solvent Yellow 2 [60-11-7], Solvent Yellow 3 [97-56-3], Solvent Yellow 7[1689-82-3], Solvent Yellow 14 [842-07-9], Disperse Orange 1[2581-69-3], Disperse Orange 3 [730-40-5], Disperse Orange 25[31482-56-1], Disperse Red 1 [2872-52-8], Disperse Red 13 [3180-81-2],Disperse Red 19 [2734-52-3], Disperse Red 50 [12223-35-7]+[40880-51-1],Disperse Yellow 3, Mordant Brown 4 [6247-28-5], Mordant Brown 6[6247-28-5], Mordant Brown 24 [6370-46-3], Mordant Brown 48 [6232-53-7],Mordant Orange 1 [2243-76-7], Pigment Red 3 [2425-85-6],4-dimethylamino-2-methylazobenzene [54-88-6],2-(4-diethylaminophenylazo)benzoic acid [76058-33-8],N-ethyl-N-(2-aminoethyl)-4-(4-nitro-phenylazo)aniline,N,N-hydroxyethyl-4-(4-nitrophenyl-azo)-2-methylaniline,N,N-hydroxyethyl-4-(4-amino-phenylazo)-2-aniline, and mixtures thereof.

The method according to the invention therefore consists in applying atleast one direct dye, contained in a dry composition, to or close tokeratin materials, and in applying a source of heat causing thermaltransfer of the direct dye(s) at the surface and/or inside the keratinmaterials. Preferably, the direct dye is applied to the keratinmaterials to be treated.

According to a first embodiment, the direct dye is applied to thekeratin materials in the form of a divided solid, in free form. Theexpression free form is understood to mean that the direct dye does notexist in a form dispersed in a matrix.

According to one variant of this first embodiment, the direct dye isdeposited in free form on a heat-resistant support. The keratinmaterial, preferably hair, is applied to this support and the whole isheated by means of an instrument which releases heat. For example, asmoothing iron or a laser may be used.

According to a second embodiment of the invention, the direct dye isapplied to the keratin materials in a divided solid form, in a non-freeform. The direct dye is said to be in a non-free form when it isdispersed in a matrix. Advantageously, the direct dye is applied in theform of a film deposited or not deposited on a support.

In the case of this embodiment, the film comprises at least onefilm-forming polymer.

The period for which the heat source is applied is such that the keratinmaterial is not substantially degraded. More particularly, the physicaland physicochemical properties of the keratin material are notsubstantially impaired. There is furthermore no substantial modificationof their natural colour, or modification of their mechanical resistanceproperties.

Thus, the higher the temperature, the shorter the duration of treatment.

By way of illustration, the duration is between 1 picosecond and 10minutes.

The heat source may be provided in a conventional manner, such as forexample a hair dryer, a hair dressing hood, a smoothing iron, a curlingiron, a pulsed or non-pulsed laser system (a high-energy UV, visible orinfrared light radiation), a heating tong system, and the like.

According to the method of the invention, a quantity of at least 0.0001g of dye is deposited, by application, per gram of keratin material whenit is in free form.

Furthermore, a quantity of at most 20 g of dye is deposited per gram ofkeratin material, more particularly at most 10 g of dye per gram ofkeratin material, and preferably at most 5 g of dye per gram of keratinmaterial when it is in free form.

Advantageously, the keratin materials to which the film comprising thedirect dye(s) is deposited are enclosed in a support which is resistantto heat under the application conditions. Furthermore, the support isaluminium foil, greaseproof paper or alternatively any syntheticmaterial with a high glass transition temperature.

The operation may be carried out lock by lock or on the whole of thefibres.

Another subject of the present invention consists of a dry compositioncomprising at least one direct dye, and preferably at least one directazo dye of formula (I) mentioned above, preferably in a state dispersedin the composition, and at least one film-forming polymer.

More particularly, the composition is provided in the form of a filmdeposited or not deposited on an appropriate support.

All the film-forming polymers are suitable for carrying out theinvention, as long as they can be deposited by coating and remaincohesive once the film has been obtained and dried.

By way of examples of such film-forming polymers, reference may be madein particular to the manual International Cosmetic Ingredient Directoryand Handbook 2000 edition, Volume 2, pages 1744 to 1747 which relates tofilm-forming compounds.

Among the polymers capable of entering into the composition of the filmscomprising the direct dye, there may be mentioned, for example, thepolymers derived from vinylpyrrolidone, polyvinyl alcohol,polyurethanes, polymers derived from caprolactam, vinyllactam, vinylacetate, polymers derived from acrylamide, polysaccharides capable offorming a film in the dry state such as cellulose derivatives, starchesand derivatives, pullulan gum, gum arabic, pectins, alginates,carrageenans, galactomannans, agars, chitosans, chitins, polymersderived from hyaluronic acid, xanthan gum, karaya gum, proteins capableof forming a film in the dry state, such as gelatin, gluten, casein,zein, gliadin, hordein and their natural or synthetic derivatives,polymers derived from silicones, amphoteric or anionic polymers whichare derived from monomers comprising at least one carboxylic, sulphonicor phosphoric functional group, acrylic copolymers of phosphorylcholine(lipidure), anion-cation complexes of the gum arabic/gelatin or gumarabic/chitosan type, or the collagen/GlycosAminoGlycan combination.

By way of suitable cationic film-forming polymers, there may bementioned more particularly the following polymers, having in general anumber-average molecular mass of between 500 and about 5 000 000:

(1) the homopolymers or copolymers derived from acrylic or methacrylicesters or amides and comprising at least one of the units of thefollowing formulae:

in which:R₁ and R₂, which are identical or different, each represent a hydrogenatom or an alkyl group having from 1 to 6 carbon atoms;R₃ denotes a hydrogen atom or a CH₃ group;A is a linear or branched alkyl group of 1 to 6 carbon atoms, or ahydroxyalkyl group of 1 to 4 carbon atoms;R₄, R₅, R₆, which are identical or different, represent an alkyl grouphaving from 1 to 18 carbon atoms or a benzyl group;X denotes a methosulphate anion or a halide such as chloride or bromide;(2) the quaternized guar gums;(3) the quaternized copolymers of vinylpyrrolidone and vinylimidazole;(4) the chitosans or their salts;the salts which can be used are in particular the acetate, lactate,glutamate, gluconate or pyrrolidonecarboxylate of chitosan.

The copolymers of the family (1) contain, in addition, one or more unitsderived from comonomers which may be chosen from the family ofacrylamides, methacrylamides, diacetone acrylamides, acrylamides andmethacrylamides substituted on the nitrogen with lower (C₁₋₄) alkyls,groups derived from acrylic or methacrylic acids or esters thereof,vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.

Thus, among these copolymers of the family (1), there may be mentioned:

-   -   the copolymers of acrylamide and dimethylamino-ethyl        methacrylate quaternized with dimethyl sulphate or with a        dimethyl halide,    -   the copolymers of acrylamide and        methacryloyloxy-ethyltrimethylammonium chloride described, for        example, in Patent Application EP-A-080976,    -   the copolymers of acrylamide and        methacryloyloxy-ethyltrimethylammonium methosulphate,    -   the vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate        copolymers, quaternized or otherwise, such as the products sold        under the name “GAFQUAT®”, by the company ISP such as for        example “GAFQUAT® 734” or “GAFQUAT® 755” or alternatively the        products called “COPOLYMER® 845, 958 and 937”. These polymers        are described in detail in French Patents 2 077 143 and 2 393        573,    -   the dimethylaminoethyl        methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers such        as the product sold under the name GAFFIX® VC 713 by the company        ISP, and    -   the quaternized vinylpyrrolidone/dimethyl-aminopropyl        methacrylamide copolymer such as in particular the product sold        under the name “GAFQUAT® HS 100” by the company ISP.

Among these compounds, there may be mentioned chitosan having a degreeof deacetylation of 90% by weight, pyrrolidone-chitosan carboxylate soldunder the name KYTAMER® PC by the company AMERCHOL.

As regards the anionic film-forming polymers, the latter generallycomprise at least one group derived from a carboxylic, sulphonic orphosphoric acid and have a number-average molecular mass of betweenabout 500 and 5 000 000.

The carboxylic groups are more particularly provided by unsaturatedmono- or dicarboxylic acid monomers such as those corresponding to theformula:

in which n is an integer from 0 to 10, A₁ denotes a methylene group,optionally linked to the carbon atom of the unsaturated group or to theneighbouring methylene group, when n is greater than 1, through aheteroatom such as oxygen or sulphur, Ra denotes a hydrogen atom, or aphenyl or benzyl group, Rb denotes a hydrogen atom, a C₁-C₄ alkyl group,in particular methyl, ethyl or carboxyl, Rc denotes a hydrogen atom or alower alkyl group, a group —CH₂—COOH, or a phenyl or benzyl group.

The preferred anionic film-forming polymers with carboxylic groups are:

A) the homo- or copolymers of acrylic or methacrylic acid or their saltsand in particular the products sold under the names VERSICOL® E or K bythe company ALLIED COLLOID and ULTRAHOLD® by the company BASF, thecopolymers of acrylic acid and of acrylamide, the sodium salts of thepolyhydroxycarboxylic acids.

B) The copolymers of acrylic or methacrylic acid with a monoethylenemonomer such as ethylene, styrene, vinyl esters, acrylic or methacrylicacid esters, optionally grafted onto a polyalkylene glycol such aspolyethylene glycol and optionally crosslinked. Such polymers aredescribed in particular in French Patent 1 222 944 and GermanApplication 2 330 956, copolymers of this type containing in their chainan acrylamide unit optionally N-alkylated and/or hydroxyalkylated asdescribed especially in Luxembourg Patent Applications 75370 and 75371.There may also be mentioned the copolymers of acrylic acid and C₁-C₄alkyl methacrylate and the terpolymers of vinylpyrrolidone, acrylic acidand C₁-C₂₀ alkyl, for example lauryl, methacrylate such as that sold bythe company ISP under the name ACRYLIDONE® LM and the methacrylicacid/ethyl acrylate/tert-butyl acrylate terpolymers such as the productsold under the name LUVIMER® 100 P by the company BASF.

C) The copolymers derived from crotonic acid such as those containing intheir chain vinyl propionate or acetate units and optionally othermonomers such as methallyl or allyl esters, vinyl ether or vinyl esterof a linear or branched saturated carboxylic acid with a longhydrocarbon chain such as those containing at least 5 carbon atoms, itbeing possible for these polymers to be optionally grafted andcrosslinked or alternatively another monomer which is a vinyl, allyl ormethallyl ester of an α- or β-cyclic carboxylic acid. Such polymers aredescribed, inter alia, in French Patents 1 222 944, 1 580 545, 2 265782, 2 265 781, 1 564 110 and 2 439 798. A commercial product enteringinto this class is the resin 28-29-30 sold by the company NATIONALSTARCH.

D) The copolymers derived from C₄-C₈ monounsaturated carboxylic acids oranhydrides chosen from:

-   -   the copolymers comprising (i) one or more itaconic, fumaric or        maleic acids or anhydrides and (ii) at least one monomer chosen        from vinyl esters, vinyl ethers, vinyl halides, phenylvinyl        derivatives, acrylic acid and its esters, the anhydride        functions of these copolymers being optionally monoesterified or        monoamidated. Such polymers are described in particular in        Patents U.S. Pat. Nos. 2,047,398, 2,723,248, 2,102,113 and        Patent GB 839805. Marketed products are especially those sold        under the names GANTREZ® AN or ES by the company ISP.    -   the copolymers comprising (i) one or more maleic, citraconic or        itaconic anhydride units and (ii) one or more monomers chosen        from allyl or methallyl esters optionally containing one or more        acrylamide, methacrylamide or α-olefin groups, acrylic or        methacrylic esters, acrylic or methacrylic acid or        vinylpyrrolidone in their chain, the anhydride functions of        these copolymers being optionally monoesterified or        monoamidated.

These polymers are, for example, described in French Patents 2 350 384and 2 357 241 by the applicant.

E) The polyacrylamides containing carboxylate groups;

F) the anionic polyurethanes, such as the product sold by BASF under thename Luviset PUR.

The polymers comprising sulphonic groups are polymers containingvinylsulphonic, styrenesulphonic, naphthalenesulphonic oracrylamidoalkylsulphonic units.

These polymers may be especially chosen from:

-   -   the salts of polyvinylsulphonic acid having a molecular mass of        between about 1000 and 100 000 as well as the copolymers with an        unsaturated comonomer such as acrylic or methacrylic acids and        their esters as well as acrylamide or its derivatives, vinyl        ethers and vinylpyrrolidone.    -   the salts of polystyrenesulphonic acid such as the sodium salts        sold for example under the name Flexan® 130 by NATIONAL STARCH.        These compounds are described in Patent FR 2 198 719.    -   the salts of polyacrylamidesulphonic acids, such as those        mentioned in Patent U.S. Pat. No. 4,128,631 and more        particularly polyacrylamidoethylpropanesulphonic acid.

According to the invention, it is also possible to use film-forminganionic polymers of the grafted silicone type comprising a polysiloxaneportion and a portion consisting of a nonsilicone organic chain, one ofthe two portions constituting the principal chain of the polymer, theother being grafted onto the said principal chain. These polymers arefor example described in patent applications EP-A-/412 704, EP-A-/412707, EP-A-/640 105 and WO 95/00578, EP-A-/582 152 and WO 93/23009 andpatents U.S. Pat. No. 4,693,935, U.S. Pat. No. 4,728,571 and U.S. Pat.No. 4,972,037.

Such polymers are, for example, the copolymers which can be obtained byfree-radical polymerization starting with a mixture of monomers,consisting of:

a) 50 to 90% by weight of tert-butyl acrylate;b) 0 to 40% by weight of acrylic acid;c) 5 to 40% by weight of silicone-containing macromer of formula:

with v being a number ranging from 5 to 700; the percentages by weightbeing calculated relative to the total weight of the monomers.

Further examples of grafted silicone polymers include in particularpolydimethylsiloxanes (PDMS) onto which are grafted, via a chain link ofthiopropylene type, mixed polymer units of poly(meth)acrylic acid typeor of poly(alkyl (meth)acrylate) type, and polydimethylsiloxanes (PDMS)onto which are grafted, via a chain link of thiopropylene type, polymerunits of poly(isobutyl(meth)acrylate) type.

It is also possible use, as film-forming polymers, functionalizedpolyurethanes, containing silicone or not.

The polyurethanes particularly sought by the present invention are thosedescribed in patents EP 0 751 162, EP 0 637 600, FR 2 743 297 and EP 0648 485 and the patents EP 0 656 021 or WO 94/03510 and EP 0 619 111.

According to the invention, the anionic film-forming polymers arepreferably chosen from the acrylic acid copolymers such as the acrylicacid/ethyl acrylate/N-tert-butylacrylamide terpolymers sold under thename ULTRAHOLD® STRONG by the company BASF, the copolymers derived fromcrotonic acid such as the vinyl acetate/vinyltert-butylbenzoate/crotonic acid terpolymers and the crotonic acid/vinylacetate/vinyl neododecanoate terpolymers sold in particular under thename Résine 28-29-30 by the company NATIONAL STARCH, the polymersderived from itaconic, fumaric and maleic acids or anhydrides with vinylesters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylicacid and its esters such as the monoesterified maleic anhydride/methylvinyl ether copolymers sold, for example, under the name GANTREZ® by thecompany ISP, the copolymers of methacrylic acid and of methylmethacrylate sold under the name EUDRAGIT® L by the company ROHM PHARMA,the copolymers of methacrylic acid and of ethyl acrylate sold under thename LUVIMER® MAEX or MAE by the company BASF and the vinylacetate/crotonic acid copolymers and the vinyl acetate/crotonic acidcopolymers grafted with polyethylene glycol sold under the nameARISTOFLEX® A by the company BASF and the polyurethane Luviset PUR® soldby the company BASF.

The anionic film-forming polymers which are most particularly preferredare those chosen from the monoesterified maleic anhydride/methyl vinylether copolymers sold under the name GANTREZ® ES 425 by the company ISP,the acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers soldunder the name ULTRAHOLD® STRONG by the company BASF, the copolymers ofmethacrylic acid and of methyl methacrylate sold under the nameEUDRAGIT® L by the company ROHM PHARMA, the vinyl acetate/vinyltert-butylbenzoate/crotonic acid terpolymers and the crotonic acid/vinylacetate/vinyl neododecanoate terpolymers sold under the name Résine28-29-30 by the company NATIONAL STARCH, the copolymers of methacrylicacid and ethyl acrylate sold under the name LUVIMER® MAEX or MAE by thecompany BASF, the vinylpyrrolidone/acrylic acid/lauryl methacrylateterpolymers sold under the name ACRYLIDONE® LM by the company ISP andthe polyurethane Luviset PUR® sold by the company BASF.

Among the amphoteric film-forming polymers which can be used, there maybe mentioned those containing B and C units distributed randomly in thepolymer chain where B denotes a unit which is derived from a monomercontaining at least one basic nitrogen atom and C denotes a unit whichis derived from an acidic monomer containing one or more carboxylic orsulphonic groups or alternatively B and C may denote groups which arederived from zwitterionic monomers of carboxybetaines or ofsulphobetaines;

B and C may also denote a cationic polymer chain containing primary,secondary, tertiary or quaternary amine groups, in which at least one ofthe amine groups carries a carboxylic or sulphonic group linked via ahydrocarbon group or alternatively B and C form part of a chain of apolymer with an α-dicarboxylic ethylene unit in which one of thecarboxylic groups has been caused to react with a polyamine containingone or more primary or secondary amine groups.

The amphoteric film-forming polymers corresponding to the definitiongiven above which are more particularly preferred are chosen from thefollowing polymers:

(1) The polymers resulting from the copolymerization of a monomerderived from a vinyl compound carrying a carboxylic group such as moreparticularly acrylic acid, methacrylic acid, maleic acid,alpha-chloroacrylic acid, and of a basic monomer derived from asubstituted vinyl compound containing at least one basic atom(preferably an amino functional group) such as more particularlydialkylaminoalkyl methacrylate and acrylate,dialkylaminoalkylmethacrylamide and -acrylamide. Such compounds aredescribed in American U.S. Pat. No. 3,836,537. There may also bementioned the sodium acrylate/acrylamidopropyltrimethylammonium chloridecopolymer sold under the name POLYQUART KE 3033 by the company HENKEL.

The vinyl compound may also be a dialkyldiallylammonium salt such asdiethyldiallylammonium chloride. The copolymers of acrylic acid and thelatter monomer are offered under the names MERQUAT 280, MERQUAT 295 andMERQUAT PLUS 3330 by the company CALGON.

(2) The polymers containing units which are derived from:

-   -   a) at least one monomer chosen from acrylamides or        methacrylamides substituted on the nitrogen atom by an alkyl        group,    -   b) at least one acidic comonomer containing one or more reactive        carboxylic groups, and    -   c) at least one basic comonomer such as esters with primary,        secondary, tertiary and quaternary amine substituents of acrylic        and methacrylic acids and the product of quaternization of        dimethylaminoethyl methacrylate with dimethyl or diethyl        sulphate.

The N-substituted acrylamides or methacrylamides more particularlypreferred are compounds whose alkyl groups contain from 2 to 12 carbonatoms and more particularly N-ethylacrylamide, N-tert-butylacrylamide,N-tert-octylacrylamide, N-octylacrylamide, N-decylacrylamide,N-dodecylacrylamide as well as the corresponding methacrylamides.

The acidic comonomers are chosen more particularly from acrylic,methacrylic, crotonic, itaconic, maleic and fumaric acids as well as thealkyl monoesters having 1 to 4 carbon atoms of maleic or fumaricanhydrides or acids.

The basic comonomers preferred are methacrylates of aminoethyl,butylaminoethyl, N,N′-dimethylaminoethyl, N-tert-butylaminoethyl.

Particularly used are the copolymers whose CTFA name (4th ed., 1991) isOctylacrylamide/acrylates/butyl-aminoethyl methacrylate copolymer suchas the products sold under the name AMPHOMER® or LOVOCRYL® 47 by thecompany NATIONAL STARCH.

(3) The partially or completely acylated and crosslinked polyaminoamidesderived from polyaminoamides of general formula:

in which R₁₀ represents a divalent group derived from a saturateddicarboxylic acid, a mono- or dicarboxylic aliphatic acid with ethylenicdouble bond, an ester of a lower alkanol having 1 to 6 carbon atoms ofthese acids or a group which is derived from the addition of any one ofthe said acids with a bis-primary or bis-secondary amine, and Z denotesa group which is derived from a bis-primary, mono- or bis-secondarypolyalkylene-polyamine and preferably represents:a) in the proportions of 60 to 100 mol %, the group

where x=2 and p=2 or 3, or alternatively x=3 and p=2 this group beingderived from diethylenetriamine, triethylenetetraamine ordipropylenetriamine;

b) in the proportions of 0 to 40 mol %, the group (IV) above, in whichx=2 and p=1 and which is derived from ethylenediamine, or the groupwhich is derived from piperazine:

c) in the proportions of 0 to 20 mol %, the group —NH—(CH₂)₆—NH— whichis derived from hexamethylenediamine, these polyamino amides beingcrosslinked by adding a bifunctional crosslinking agent chosen from theepihalohydrins, diepoxides, dianhydrides, bis-unsaturated derivatives,by means of 0.025 to 0.35 mol of crosslinking agent per amine group ofthe polyamino amide and acylated by the action of acrylic acid,chloroacetic acid or of an alkanesultone or of their salts.

The saturated carboxylic acids are preferably chosen from the acidshaving 6 to 10 carbon atoms such as adipic, 2,2,4-trimethyladipic and2,4,4-trimethyladipic acids, terephthalic acid, the acids with ethylenedouble bond such as for example acrylic, methacrylic and itaconic acids.

The alkanesultones used in the acylation are preferably propane- orbutanesultone, the salts of the acylating agents are preferably thesodium or potassium salts.

(4) The polymers containing zwitterionic units of formula:

in which R₁₁ denotes a polymerizable unsaturated group such as anacrylate, methacrylate, acrylamide or methacrylamide group, y and zrepresent an integer from 1 to 3, R₁₂ and R₁₃ represent a hydrogen atomor a methyl, ethyl or propyl group, R₁₄ and R₁₅ represent a hyrogen atomor an alkyl group such that the sum of the carbon atoms in R₁₄ and R₁₅does not exceed 10.

The polymers comprising such units may also comprise units derived fromnonzwitterionic monomers such as dimethyl- or diethylaminoethyl acrylateor methacrylate or alkyl acrylates or methacrylates, acrylamides ormethacrylamides or vinyl acetate.

By way of example, there may be mentioned the copolymers of methylmethacrylate/N,N-dimethylcarboxyaminoethyl methacrylate.

(5) The polymers derived from chitosan containing monomeric unitscorresponding to the following formulae:

the (D) unit being present in proportions of between 0 and 30%, the (E)unit in proportions of between 5 and 50% and the (F) unit in proportionsof between 30 and 90%, it being understood that in this (F) unit, R₁₆represents a group of formula:

in which if q=0, R₁₇, R₁₈ and R₁₉, which are identical or different,each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or aminoresidue, a monoalkylamine residue or a dialkylamine residue optionallyinterrupted by one or more nitrogen atoms and/or optionally substitutedwith one or more amine, hydroxyl, carboxyl, alkylthio or sulphonicgroups, or an alkylthio residue whose alkyl group carries an aminoresidue, at least one of the R₁₇, R₁₈ and R₁₉ groups being in this casea hydrogen atom;

or if q=1, R₁₇, R₁₈ and R₁₉ each represent a hydrogen atom, as well asthe salts formed by these compounds with bases or acids.

(6) The polymers corresponding to the general formula (VI) are describedfor example in French Patent 1 400 366 and comprising the repeating unitbelow:

in which R₂₀ represents a hydrogen atom, a CH₃O, CH₃CH₂O or phenylgroup, R₂₁ denotes a hydrogen atom or a lower alkyl group such as methylor ethyl, R₂₂ denotes a hydrogen atom or a C₁-C₆ lower alkyl group suchas methyl or ethyl, R₂₃ denotes a C₁-C₆ lower alkyl group such as methylor ethyl or a group corresponding to the formula: —R₂₄—N(R₂₂)₂, R₂₄representing a group —CH₂—CH₂—, —CH₂—CH₂—CH₂— or —CH₂—CH(CH₃)—, R₂₂having the meanings mentioned above.

(7) The polymers derived from the N-carboxyalkylation of chitosan suchas N-carboxymethyl chitosan or N-carboxybutyl chitosan.

(8) The amphoteric polymers of the -D-X-D-X— type chosen from:

a) the polymers obtained by the action of chloroacetic acid or sodiumchloroacetate on the compounds containing at least one unit of formula:

-D-X-D-X-D-  (VII)

where D denotes a group

and X denotes the symbol E or E′, E and E′, which are identical ordifferent, denote a bivalent group which is an alkylene group with alinear or branched chain containing up to 7 carbon atoms in theprincipal chain which is unsubstituted or substituted with hydroxylgroups and which may contain, in addition, oxygen, nitrogen or sulphuratoms, 1 to 3 aromatic and/or heterocyclic rings; the oxygen, nitrogenand sulphur atoms being present in the form of ether, thioether,sulphoxide, sulphone, sulphonium, alkylamine or alkenylamine groups, orhydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide,alcohol, ester and/or urethane groups.

b) The polymers of formula:

-D-X-D-X-  (VII′)

where D denotes a group

and X denotes the symbol E or E′ and, at least once, E′; E having themeaning indicated above and E′ is a bivalent group which is an alkylenegroup with a linear or branched chain having up to 7 carbon atoms in theprincipal chain, which is unsubstituted or substituted with one or morehydroxyl groups and containing one or more nitrogen atoms, the nitrogenatom being substituted with an alkyl chain optionally interrupted by anoxygen atom and necessarily containing one or more carboxyl functionalgroups or one or more hydroxyl functional groups and betainized byreaction with chloroacetic acid or sodium chloroacetate.

(9) The (C₁-C₅)alkyl vinyl ether/maleic anhydride copolymers partiallymodified by semiamidation with an N,N-dialkylaminoalkylamine such asN,N-dimethylamino-propylamine or by semiesterification with anN,N-dialkylaminoalkanol. These copolymers may also contain other vinylcomonomers such as vinylcaprolactam.

The preferred amphoteric film-forming polymers are those of the family(3) such as the copolymers whose CTFA name isOctylacrylamide/acrylates/butylaminoethyl methacrylate copolymer such asthe products sold under the names AMPHOMER®, AMPHOMER® LV 71 orLOVOCRYL® 47 by the company NATIONAL STARCH and those of the family (4)such as the butyl methacrylate/N,N-dimethylcarboxyaminoethylmethacrylate copolymers.

The nonionic film-forming polymers which can be used according to thepresent invention are chosen for example from:

-   -   the homopolymers of vinyl acetate;    -   the copolymers of vinyl acetate and acrylic ester;    -   the copolymers of vinyl acetate and ethylene;    -   the copolymers of vinyl acetate and maleic ester, for example        dibutyl maleate;    -   the copolymers of acrylic esters such as for example the        copolymers of alkyl acrylates and alkyl methacrylates such as        the products offered by the company ROHM & HAAS under the names        PRIMAL® AC-261 K and EUDRAGIT® NE 30 D, by the company BASF        under the name 8845, by the company HOECHST under the name        APPRETAN® N9212;    -   the copolymers of acrylonitrile and of a nonionic monomer chosen        for example from butadiene and alkyl (meth)acrylates; there may        be mentioned the products offered under the name CJ 0601 B by        the company ROHM & HAAS;    -   the homopolymers of styrene;    -   the copolymers of styrene and alkyl (meth)acrylate such as the        products MOWILITH® LDM 6911, MOWILITH® DM 611 and MOWILITH®LDM        6070 offered by the company HOECHST, the products RHODOPAS® SD        215 and RHODOPAS® DS 910 offered by the company RHODIA CHIMIE;    -   the copolymers of styrene, alkyl methacrylate and alkyl        acrylate;    -   the nonionic polyurethanes;    -   the copolymers of styrene and butadiene;    -   the copolymers of styrene, butadiene and vinylpyridine;    -   the copolymers of alkyl acrylate and urethane;    -   the polyamides;    -   the homopolymers and copolymers of vinyllactam.

The alkyl groups of the nonionic polymers mentioned above preferablyhave from 1 to 6 carbon atoms.

According to the present invention, the film-forming polymers arepreferably nonionic polymers, and better still nonionic polymers withvinyllactam units. They are described in particular in Patents U.S. Pat.No. 3,770,683, U.S. Pat. No. 3,929,735, U.S. Pat. No. 4,521,504, U.S.Pat. No. 5,158,762, U.S. Pat. No. 5,506,315 and in Patent ApplicationsWO 94/121148, WO 96/06592 and WO 96/10593. They may be provided inpulverulent form or in the form of a solution or a suspension.

The homopolymers or copolymers with vinyllactam units comprise units offormula (IX):

in which n is independently 3, 4 or 5.

The number-average molecular mass of the polymers with vinyllactam unitsis generally greater than about 5000, preferably between 10 000 and 1000 000 approximately, more preferably between 10 000 and 100 000approximately.

It is possible to use, in particular, as film-forming polymer, in thepresent invention, polyvinyl-pyrrolidones such as those marketed underthe name Luviskol® K30 by the company BASF; polyvinylcaprolactams suchas those marketed under the name Luviskol® PLUS by the company BASF;poly(vinylpyrrolidone/vinyl acetate) copolymers such as those marketedunder the name PVPVA® S630L by the company ISP, Luviskol® VA 73, VA 64,VA 55, VA 37 and VA 28 by the company BASF; andpoly(vinylpyrrolidone/vinyl acetate/vinyl propionate) terpolymers suchas for example those marketed under the name Luviskol® VAP 343 by thecompany BASF.

According to this second embodiment, the composition, in film form, maycomprise at least one plasticizer.

The plasticizers conventionally used in the field may be used in thecomposition.

However, by way of more specific examples, there may be mentioned, interalia, urea, glycerine, sorbitol, mono- and/or disaccharides, dipropyleneglycol, butylene glycol, pentylene glycol or polyethylene glycol, benzylalcohol, or mixtures thereof.

Advantageously, the film may contain at least one formulation adjuvantand/or cosmetic active agent chosen for example from dispersing agentssuch as alkali metal lignosulphonates, antioxidants, pH-regulatingagents, perfumes, silicones, ceramides.

Usually, the content of adjuvant in the composition represents, foreach, from 0.01 to 20% each; the total content of additives, if they arepresent, not exceeding 80% by weight of the dry solid composition.

The composition according to the invention may additionally be in theform of a film deposited or not deposited on a support.

If the support is present, the latter is advantageously chosen fromcompounds which are not degraded under the conditions for carrying outthe method.

The support is chosen from compounds which do not become solubilizedunder the conditions for preparing the said film. Thus, the support isnot soluble in an aqueous medium.

Furthermore, the support may be chosen from compounds which conductelectricity or from compounds which are electrical insulators.

The water-soluble or water-insoluble support may thus be made of amaterial chosen from polyurethanes, thermoplastic elastomers of the typeincluding styrene-butadiene-styrene, styrene-ethylene-butadiene-styrene,ethylene-vinyl acetate, or coether ester, poly-ethylenes,polypropylenes, or silicones.

Such supports are sold in particular under the trade marks: BAYDUR®,DALTOFLEX®, UROFLEX®, HYPERLAST®, INSPIRE®, DESMOPAN®, ESTANE®,LASTANE®, TEXIN®, CARIFLEX®, KRATON®, SOLPRENE®, ELVAX®, ESCORENE®,OPTENE®, ARNITEL®, HYTREL®, or RITEFLEX®.

It would not be excluded to choose, as support, an inorganic compoundsuch as for example aluminium.

It is specified that the thickness of the support on which thecomposition is deposited preferably has a thickness which allows easyuse for dyeing the keratin materials (easy folding, sufficient solidityto allow several applications with several foldings and unfoldings).

Usually, the thickness of the support is preferably between 0.01 mm and2 mm, and preferably between 0.02 and 0.2 mm.

Furthermore, when the composition is deposited on a support, thethickness of the film made of the composition is usually between 20 μmand 1000 μm, and preferably between 50 μm and 200 μm.

In the case where the composition is in the form of a film not depositedon a support, the thickness of the film made of the composition is closeto 0.01 mm to 2 mm, preferably 0.02 to 0.2 mm.

Another subject of the invention consists of a method for preparing acomposition in the form of a film.

More particularly, a method consists in carrying out the followingsteps:

a) a composition comprising at least one dye of formula (I), at leastone film-forming polymer and at least one solvent is prepared;b) a film made of the composition thus obtained is deposited on anappropriate support;c) the solvent is evaporated.

The solvent entering into the composition is chosen from the compoundswhich solubilize or disperse at least the film-forming polymer. In thelatter case, the film-forming polymers are in the form of dispersions ofsolid or liquid particles of polymer (latex or pseudolatex).

Moreover, the solvent furthermore has a boiling point less than thesublimation temperature of the dye and less than the degradationtemperature of the film-forming polymer. Advantageously, the boilingpoint of the solvent is less than or equal to 110° C.

By way of examples of solvents which can be used, there may be mentionedfor example water, ethanol, acetone, isopropanol, ethyl acetate,dichloromethane, ethyl ether and the like.

Preferably, the composition comprises from 5 to 99.9% by weight ofsolvent.

It should be noted, advantageously, that the composition comprises from0.0001 to 60% of direct dye.

Moreover, according to a particular embodiment, the compositioncomprises from 0.01 to 80% by weight of film-forming polymer.

Once the composition has been obtained, it is deposited on anappropriate support, such as for example a non-rough and horizontalsupport of the heating or non-heating bed or marble type.

It should be specified that, advantageously, the composition isdeposited directly on the support with which the composition is intendedto be used for dyeing, if such a variant is chosen.

It is preferable for the thickness of the composition deposited to berelatively uniform.

Furthermore, the thickness of the composition deposited is such that afilm is obtained, preferably after evaporation of the solvent, which canbe handled at room temperature (more particularly between 15 and 30°C.). Without limitation, the thickness of the composition depositedvaries in general from 0.01 to 2 mm, preferably from 0.02 to 2 mm.

The composition is deposited in a conventional manner, without, butpreferably with, an apparatus which makes it possible to obtain asubstantially uniform film thickness.

After depositing the composition, the solvent is evaporated in aconventional manner.

The film obtained is then separated from its support and then depositedon the materials to be treated.

Concrete but nonlimiting examples of the invention will now bepresented.

EXAMPLES 1. Preparation of a Dyed Film

The following mixture is prepared, with stirring for 20 minutes

Constituent Concentration Dye 2% Hydroxypropylcellulose sold under the1.5% name Klucel MF by the company Aqualon Ethanol qs. 100%and deposited on a heating plate at 60° C. The dyed film is formed byevaporation of the ethanol.

2. Hair Dyeing

The film obtained above is applied to natural hair which is 900 white.

Each lock is then covered with aluminium foil.

Heat is applied by means of a Japanese smoothing iron

Thermal Effect Iron (temperature and duration indicated in the tablebelow).

At the end of the treatment, the locks are dyed.

No rinsing is necessary.

The colour of each lock is then measured (Minolta CM3600dspectrocolorimeter, specular components included, angle 10°, illuminantD65).

3. Colorimetric Results

T T° C. (min) L* Control — — 61.3 Dye 1 180 5 39.5 Dye 2 180 5 36.8 Dye3 180 5 31.3 Dye 7 180 5 42.3 Dye 4 180 5 25.4 Dye 5 180 5 31.3 Dye 6185 1 39.0

1. Use, for dyeing in particular human keratin materials, by dry thermaltransfer, of at least one direct dye.
 2. Use according to the precedingclaim, characterized in that the direct dye is chosen from acridine,acridone, anthranthrone, anthrapyrimidine, anthraquinone, azine, azo,azomethine, benzanthrone, benzimidazole, benzimidazolone, benzindole,benzoxazole, benzopyran, benzothiazole, benzoquinone, bisazine,bisisoindoline, carboxanilide, coumarin, cyanine (such as for exampleazacarbocyanine, diazacarbocyanine, diazahemicyanine, hemicyanine,tetraazacarbocyanine), diazine, diketopyrrolopyrrole, dioxazine,diphenylamine, diphenylmethane, dithiazine, flavonoid such asflavanthrone and flavone, fluoroindine, formazan, hydrazone inparticular arylhydrazone, hydroxyketone, indamine, indanthrone,indigoid, and pseudo-indigoid, indophenol, indoaniline, isoindoline,isoindolinone, isoviolanthrone, lactone, methine, naphthalimide,naphthanilide, naphtholactam, naphthoquinone, nitro(hetero)aromatic,oxadiazole, oxazine, perilone, perinone, perylene, phenazine,phenothiazine, phthalocyanine, polyene/carotenoid, porphyrine,pyranthrone, pyrazoloanthrone, pyrazolone, pyrimidinoanthrone, pyronine,quinacridone, quinoline, quinophthalone, squarane, stilbene,tetrazolium, thiazine, thioindigo, thiopyronine, triarylmethane andxanthene dyes, alone or as mixtures.
 3. Use according to either of thepreceding claims, characterized in that the direct dye is a direct azodye of the following formula (I):

in which: n and n′, which are identical or different, represent aninteger between 1 and 5 inclusive, R, which are identical or not, R′,which are identical or not, independently of each other, represent: ahydrogen atom; a linear, branched or cyclic, saturated, unsaturated oraromatic, C₁-C₃₀ hydrocarbon chain, optionally substituted with one ormore halogen atoms; with one or more groups, which are identical or not,chosen from the groups hydroxyl; nitro; cyano; carboxylic acid; allyl;haloallyl; C₁-C₁₀ alkoxy; (C₁-C₄)alkylcarbonyl(C₁-C₄)amino;(C₁-C₄)alkylaminocarbonyl; hydrogenocarbonylamino;(C₁-C₄)alkylsulphonylamino; (C₁-C₄)alkoxycarbonylamino;(C₁-C₄)alkoxycarbonyl; (C₁-C₄)alkylcarbonyl(C₁-C₄)alkoxycarbonyl; CF₃;amino; amino optionally substituted with one or more radicals which areidentical or different, C₁-C₁₀ alkyl, C₁₋₁₀ hydroxyalkyl,alkoxy-(C₁-C₁₀)alkyl, C₁-C₁₀ aminoalkyl, (C₁-C₁₀)(di)alkyl-amino(C₁-C₁₀)alkyl, C₁-C₁₀ cyanoalkyl, C₆-C₃₀ aryl,(C₆-C₃₀)aryl(C₁-C₄)alkyl, (C₄-C₃₀)cyclo-(C₁-C₁₂)alkyl,(C₁-C₄)alkylcarbonyl, (C₁-C₄)alkyl-carboxy(C₁-C₄)alkyl, allyl,haloallyl; optionally interrupted or attached to the aromatic ring viaone or more heteroatoms and/or groups comprising one or more heteroatomschosen from oxygen, sulphur, nitrogen; a group hydroxyl; C₁-C₄ alkoxy;carboxylic acid; amino; amino substituted with one or more radicals,which are identical or different, chosen from the radicals C₁-C₄ alkyl,C₂-C₄ alkenyl, C₁-C₄ cyanoalkyl, C₁-C₄ hydroxyalkyl, C₆-C₃₀ aryl,(C₆-C₃₀)aryl(C₁-C₄)alkyl, allyl, (C₁-C₄)alkoxy(C₁-C₄)alkyl,(C₄-C₃₀)cyclo(C₁-C₁₂)-alkyl, (C₁-C₄)alkylcarbonyl,(C₁-C₄)alkyl-carboxy(C₁-C₄)alkyl, haloallyl, C₃-C₄ aminoalkyl,(C₁-C₄)(di)alkylamino(C₁-C₄)alkyl, (C₁-C₄)alkyl-sulphonyl,(C₁-C₄)alkoxycarbonyl; halogen; allyl; hydrogenocarbonyl;trifluoromethyl; nitro; cyano; it being understood that at least one ofthe radicals R or R′ represents a group hydroxyl; nitro; cyano; amino;amino optionally substituted with one or more radicals, two radicals Rcarried by two adjacent carbon atoms or two radicals R′ carried by twoadjacent carbon atoms may form with the aromatic ring carrying thecarbon atoms to which each is attached a fused ring of the naphthalenetype optionally substituted with an aminosulphonyl or(C₁-C₄)alkyl(C₁-C₄)aminosulphonyl group.
 4. Use according to thepreceding claim, characterized in that the direct azo dye corresponds tothe following formula (Ia):

in which: R′₁ represents a hydrogen atom, an amino group or a hydroxylgroup; R′₂ represents a hydrogen atom, a halogen atom, a carboxylic acidgroup, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, an allyl group or aC₁-C₄ aminocarbonylalkyl group; R′₃ represents a hydrogen atom, ahydroxyl group or a group of the NR″₁R″₂ type where R″₁ and R″₂represent, independently of each other, a hydrogen atom, a C₁-C₄ alkylgroup, a C₂-C₄ alkenyl group, a C₁-C₄ cyanoalkyl group, a C₁-C₄hydroxyalkyl group, a C₆-C₃₀ aryl group, a (C₆-C₃₀)aryl(C₁-C₄)alkylgroup, an allyl group, a (C₁-C₄)alkoxy(C₁-C₄)alkyl group, a(C₄-C₃₀)cyclo(C₁-C₁₂)alkyl group, a (C₁-C₄)alkyl-carbonyl group, a(C₁-C₄)alkylcarboxy(C₁-C₄)alkyl group or a haloallyl group, a C₁-C₄aminoalkyl group, a (C₁-C₄)(di)alkylamino(C₁-C₄)alkyl group; R′₂ and R′₃may form, with the benzene ring, a fused ring of the naphthalene typeoptionally substituted with a group —SO₂—NHR where R represents ahydrogen atom or an optionally substituted C₁-C₄ alkyl chain; R′₄represents a hydrogen atom, a halogen atom, a hydroxyl group, a C₁-C₄alkyl group, a C₁-C₄ alkoxy group, a (C₁-C₄)alkoxy(C₁-C₄)alkyl group;R′₅ represents a hydrogen atom, a halogen atom, a hydroxyl group, anamino group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a(C₁-C₄)alkylcarbonylamino group, a formylamino group, a(C₁-C₄)alkylsulphonylamino group, a (C₁-C₄)alkoxycarbonylamino group ora CF₃ group; R′₄ and R′₅ may form, with the benzene ring, a fused ringof the naphthalene type; R₅ represents a hydrogen atom, a halogen atom,a carboxylic acid group, a hydroxyl group, an amino group, a cyano groupor a C₁-C₄ alkyl group; R₄ represents a hydrogen atom or a nitro group;R₃ represents a hydrogen atom, a C₁-C₄ alkyl group, a C₁-C₄ alkoxygroup, a (C₄-C₃₀)cyclo(C₁-C₁₂)alkyl group, a C₂-C₄ alkenyl group, aC₁-C₄ alkoxycarbonyl group, a (C₁-C₄)alkylcarbonyl group, a(C₁-C₄)alkoxycarbonyl(C₁-C₄)alkoxycarbonyl group, a(C₁-C₄)alkylcarbonyl(C₁-C₄)alkoxycarbonyl group, an aryl group, an aminogroup, a nitro group, a cyano group or a CF₃ group; R₂ represents ahydrogen atom, a nitro group or a C₁-C₄ alkyl group; R₁ represents ahydrogen atom, a halogen atom, a hydroxyl group, a nitro group or acyano group; it being understood that at least one of the radicals R′₁to R′ 5 and R₁ to R₅ represents a group hydroxyl; nitro; cyano; amino;amino optionally substituted with one or more radicals.
 5. Method fordyeing in particular human keratin materials, characterized in that atleast one direct dye contained in a dry composition is applied to orclose to keratin materials, and in that a source of heat causing thethermal transfer of the direct dye(s) at the surface and/or inside thekeratin materials is applied.
 6. Method according to either of claims 5and 6, characterized in that the direct dye is chosen from acridine,acridone, anthranthrone, anthrapyrimidine, anthraquinone, azine, azo,azomethine, benzanthrone, benzimidazole, benzimidazolone, benzoindole,benzoxazole, benzopyran, benzothiazole, benzoquinone, bisazine,bisisoindoline, carboxanilide, coumarin, cyanine (such as for exampleazacarbocyanine, diazacarbocyanine, diazahemicyanine, hemicyanine,tetraazacarbocyanine), diazine, diketopyrrolopyrrole, dioxazine,diphenylamine, diphenylmethane, dithiazine, flavonoid such asflavanthrone and flavone, fluoroindine, formazan, hydrazone inparticular arylhydrazone, hydroxyketone, indamine, indanthrone,indigoid, and pseudo-indigoid, indophenol, indoaniline, isoindoline,isoindolinone, isoviolanthrone, lactone, methine, naphthalimide,naphthanilide, naphtholactam, naphthoquinone, nitro(hetero)aromatic,oxadiazole, oxazine, perilone, perinone, perylene, phenazine,phenothiazine, phthalocyanine, polyene/carotenoid, porphyrine,pyranthrone, pyrazoloanthrone, pyrazolone, pyrimidinoanthrone, pyronine,quinacridone, quinoline, quinophthalone, squarane, stilbene,tetrazolium, thiazine, thioindigo, thiopyronine, triarylmethane andxanthene dyes, alone or as mixtures.
 7. Method according to either ofclaims 5 and 6, characterized in that the direct dye is an azo dye ofthe following formula (I):

in which: n and n′, which are identical or different, represent aninteger between 1 and 5 inclusive, R, which are identical or not, R′,which are identical or not, independently of each other, represent: ahydrogen atom; a linear, branched or cyclic, saturated, unsaturated oraromatic, C₁-C₃₀ hydrocarbon chain, optionally substituted with one ormore halogen atoms; with one or more groups, which are identical or not,chosen from the groups hydroxyl; nitro; cyano; carboxylic acid; allyl;haloallyl; C₁-C₁₀ alkoxy; (C₁-C₄)alkylcarbonyl(C₁-C₄)amino;(C₁-C₄)alkylaminocarbonyl; hydrogenocarbonylamino;(C₁-C₄)alkylsulphonylamino; (C₁-C₄)alkoxycarbonylamino;(C₁-C₄)alkoxycarbonyl; (C₁-C₄)alkylcarbonyl(C₁-C₄)alkoxycarbonyl; CF₃;amino; amino optionally substituted with one or more radicals which areidentical or different, C₁-C₁₀ alkyl, C₁-C₁₀ hydroxyalkyl,alkoxy-(C₁-C₁₀)alkyl, C₁-C₁₀ aminoalkyl,(C₁-C₁₀)(di)alkyl-amino(C₁-C₁₀)alkyl, C₁-C₁₀ cyanoalkyl, C₆-C₃₀ aryl,(C₆-C₃₀)aryl(C₁-C₄)alkyl, (C₄-C₃₀) C₄-C₁₀-(C₁-C₁₂)alkyl,(C₁-C₄)alkylcarbonyl, (C₁-C₄)alkyl-carboxy(C₁-C₄)alkyl, allyl,haloallyl; optionally interrupted or attached to the aromatic ring viaone or more heteroatoms and/or groups comprising one or more heteroatomschosen from oxygen, sulphur, nitrogen; a group hydroxyl; C₁-C₄ alkoxy;carboxylic acid; amino; amino substituted with one or more radicals,which are identical or different, chosen from the radicals C₁-C₄ alkyl,C₂-C₄ alkenyl, C₁-C₄ cyanoalkyl, C₁-C₄ hydroxyalkyl, C₆-C₃₀ aryl,(C₆-C₃₀)aryl(C₁-C₄)alkyl, allyl, (C₁-C₄)alkoxy(C₁-C₄)alkyl,(C₄-C₃₀)cyclo(C₁-C₁₂)-alkyl, (C₁-C₄)alkylcarbonyl,(C₁-C₄)alkyl-carboxy(C₁-C₄)alkyl, haloallyl, C₁-C₄ aminoalkyl,(C₁-C₄)(di)alkylamino(C₁-C₄)alkyl, (C₁-C₄)alkyl-sulphonyl,(C₁-C₄)alkoxycarbonyl; halogen; allyl; hydrogenocarbonyl;trifluoromethyl; nitro; cyano; it being understood that at least one ofthe radicals R or R′ represents a group hydroxyl; nitro; cyano; amino;amino optionally substituted with one or more radicals; two radicals Rcarried by two adjacent carbon atoms or two radicals R′ carried by twoadjacent carbon atoms may form with the aromatic ring carrying thecarbon atoms to which each is attached a fused ring of the naphthalenetype optionally substituted with an aminosulphonyl or(C₁-C₄)alkyl(C₁-C₄)aminosulphonyl group.
 8. Method according to thepreceding claim, characterized in that the direct dye corresponds to thefollowing formula (Ia):

in which: R′₁ represents a hydrogen atom, an amino group or a hydroxylgroup; R′₂ represents a hydrogen atom, a halogen atom, a carboxylic acidgroup, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, an allyl group or aC₁-C₄ aminocarbonylalkyl group; R′₃ represents a hydrogen atom, ahydroxyl group or a group of the NR″₁R″₂ type where R″₁ and R″₂represent, independently of each other, a hydrogen atom, a C₁-C₄ alkylgroup, a C₂-C₄ alkenyl group, a C₁-C₄ cyanoalkyl group, a C₁-C₄hydroxyalkyl group, a C₆-C₃₀ aryl group, a (C₆-C₃₀)aryl(C₁-C₄)alkylgroup, an allyl group, a (C₁-C₄)alkoxy(C₁-C₄)alkyl group, a(C₄-C₃₀)cyclo(C₁-C₁₂)alkyl group, a (C₁-C₄)alkyl-carbonyl group, a(C₁-C₄)alkylcarboxy(C₁-C₄)alkyl group or a haloallyl group, a C₁-C₄aminoalkyl group, a (C₁-C₄)(di)alkylamino(C₁-C₄)alkyl group; R′₂ and R′₃may form, with the benzene ring, a fused ring of the naphthalene typeoptionally substituted with a group —SO₂—NHR where R represents ahydrogen atom or an optionally substituted C₁-C₄ alkyl chain; R′₄represents a hydrogen atom, a halogen atom, a hydroxyl group, a C₁-C₄alkyl group, a C₁-C₄ alkoxy group, a (C₁-C₄)alkoxy(C₁-C₄)alkyl group;R′₅ represents a hydrogen atom, a halogen atom, a hydroxyl group, anamino group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a(C₁-C₄)alkylcarbonylamino group, a formylamino group, a(C₁-C₄)-alkylsulphonylamino group, a (C₁-C₄)alkoxy-carbonylamino groupor a CF₃ group; R′₄ and R′₅ may form, with the benzene ring, a fusedring of the naphthalene type; R₅ represents a hydrogen atom, a halogenatom, a carboxylic acid group, a hydroxyl group, an amino group, a cyanogroup or a C₁-C₄ alkyl group; R₄ represents a hydrogen atom or a nitrogroup; R₃ represents a hydrogen atom, a C₁-C₄ alkyl group, a C₁-C₄alkoxy group, a (C₄-C₃₀)cyclo(C₁-C₁₂)alkyl group, a C₂-C₄ alkenyl group,a C₁-C₄ alkoxycarbonyl group, a (C₁-C₄)alkylcarbonyl group, a(C₁-C₄)alkoxycarbonyl(C₁-C₄)alkoxycarbonyl group, a(C₁-C₄)alkylcarbonyl(C₁-C₄)alkoxycarbonyl group, an aryl group, an aminogroup, a nitro group, a cyano group or a CF₃ group; R₂ represents ahydrogen atom, a nitro group or a C₁-C₄ alkyl group; R₁ represents ahydrogen atom, a halogen atom, a hydroxyl group, a nitro group or acyano group; it being understood that at least one of the radicals R′₁to R′₅ and R₁ to R₅ represents a group hydroxyl; nitro; cyano; amino;amino optionally substituted with one or more radicals.
 9. Methodaccording to the preceding claim, characterized in that R₁, R₂, R₁, R₂,R₄ represent a hydrogen atom.
 10. Method according to any one of claims7 to 9, characterized in that R′₃ represents a hydrogen atom, a group ofthe NR″₁R″₂ type where R″₁ and R″₂ represent, independently of eachother, a hydrogen atom, a C₁-C₄ alkyl group, a C₁-C₄ cyanoalkyl group, aC₁-C₄ hydroxy-alkyl group, a C₁-C₄ aminoalkyl group.
 11. Methodaccording to any one of claims 7 to 10, characterized in that R′₄represents a hydrogen atom; R′₅ represents a hydrogen atom, a C₁-C₄alkyl group; R′₄ and R′₅ can form, with the benzene ring, a fused ringof the naphthalene type.
 12. Method according to any one of claims 7 to11, characterized in that R₃ represents an amino group or a nitro group.13. Method according to any one of claims 7 to 12, characterized in thatR₅ represents a hydrogen atom; a halogen atom; an amino group. 14.Method according to any one of claims 5 to 13, characterized in that thedirect dye is chosen from compounds having an enthalpy of evaporationless than or equal to 200 kJ/mol.
 15. Method according to any one ofclaims 5 to 14, characterized in that the azo dye is chosen from thefollowing dyes: Solvent Brown 1 [6416-57-5], Solvent Orange 1[2051-85-6], Solvent Orange 7 [3118-97-6], Solvent Yellow 2 [60-11-7],Solvent Yellow 3 [97-56-3], Solvent Yellow 7 [1689-82-3], Solvent Yellow14 [842-07-9], Disperse Orange 1 [2581-69-3], Disperse Orange 3[730-40-5], Disperse Orange 25 [31482-56-1], Disperse Red 1 [2872-52-8],Disperse Red 13 [3180-81-2], Disperse Red 19 [2734-52-3], Disperse Red50 [12223-35-7]+[40880-51-1], Disperse Yellow 3, Mordant Brown 4[6247-28-5], Mordant Brown 6 [6247-28-5], Mordant Brown 24 [6370-46-3],Mordant Brown 48 [6232-53-7], Mordant Orange 1 [2243-76-7], Pigment Red3 [2425-85-6], 4-dimethylamino-2-methylazobenzene [54-88-6],2-(4-diethylaminophenylazo)benzoic acid [76058-33-8];N-ethyl-N-(2-aminoethyl)-4-(4-nitrophenylazo)aniline;N,N-hydroxyethyl-4-(4-nitrophenylazo)-2-methylaniline;N,N-hydroxyethyl-4-(4-aminophenylazo)-2-aniline; and mixtures thereof.16. Method according to the preceding claim, characterized in that thesource of heat is at a temperature between 100 and 500° C.
 17. Methodaccording to any one of claims 5 to 16, characterized in that theduration is such that the keratin material is not substantiallydegraded.
 18. Method according to the preceding claim, characterized inthat the duration is between 1 picosecond and 10 minutes.
 19. Methodaccording to any one of claims 5 to 18, characterized in that a quantityof at least 0.0001 g of dye is deposited by application per gram ofkeratin material in free form.
 20. Method according to any one of claims5 to 19, characterized in that a quantity of at most 20 g of dye isdeposited by application per gram of keratin material, more particularlyat most 10 g of dye per gram of keratin material, and preferably at most5 g of dye per gram of keratin material when it is in free form. 21.Method according to any one of claims 5 to 20, characterized in that thedirect dye is applied to the keratin materials in the form of a dividedsolid, in a free or non-free form.
 22. Method according to any one ofclaims 5 to 20, characterized in that the direct dye is applied to thekeratin materials in the form of a film.
 23. Method according to thepreceding claim, characterized in that the film comprises at least onefilm-forming polymer.
 24. Method according to either of claims 22 and23, characterized in that the film comprises at least one plasticizer.25. Method according to any one of claims 22 to 24, characterized inthat the film is deposited on a support which is not degraded under theconditions for carrying out the method.
 26. Dry composition, in the formof a divided or undivided solid comprising: at least one azo dye, in thedispersed state in the composition, of formula (I):

in which: n and n′, which are identical or different, represent aninteger between 1 and 5 inclusive, R, which are identical or not, R′,which are identical or not, independently of each other, represent: ahydrogen atom; a linear, branched or cyclic, saturated, unsaturated oraromatic, C₁-C₃₀ hydrocarbon chain, optionally substituted with one ormore halogen atoms; with one or more groups, which are identical or not,chosen from the groups hydroxyl; nitro; cyano; carboxylic acid; allyl;haloallyl; C₁-C₁₀ alkoxy; (C₁-C₄)alkylcarbonyl(C₁-C₄)amino;(C₁-C₄)alkylaminocarbonyl; hydrogenocarbonylamino;(C₁-C₄)alkylsulphonylamino; (C₁-C₄)alkoxycarbonylamino;(C₁-C₄)alkoxycarbonyl; (C₁-C₄)alkylcarbonyl(C₁-C₄)alkoxycarbonyl; CF₃;amino; amino optionally substituted with one or more radicals which areidentical or different, C₁-C₁₀ alkyl, C₁-C₁₀ hydroxyalkyl,alkoxy-(C₁-C₁₀)alkyl, C₁-C₁₀ aminoalkyl, (C₁-C₁₀)-(di)alkylamino(C₁-C₁₀)alkyl, C₁-C₁₀ cyanoalkyl, C₆-C₃₀ aryl, (C₆-C₃₀)aryl(C₁-C₄)alkyl,(C₄-C₃₀)-cyclo(C₁-C₁₂)alkyl, (C₁-C₄)alkylcarbonyl, —(C₁-C₄)-alkylcarboxy(C₁-C₄)alkyl, allyl, haloallyl; optionally interrupted or attached tothe aromatic ring via one or more heteroatoms and/or groups comprisingone or more heteroatoms chosen from oxygen, sulphur, nitrogen; a grouphydroxyl; C₁-C₄ alkoxy; carboxylic acid; amino; amino substituted withone or more radicals, which are identical or different, chosen from theradicals C₁-C₄ alkyl, C₂-C₄ alkenyl, C₁-C₄ cyanoalkyl, C₁-C₄hydroxyalkyl, C₆-C₃₀ aryl, (C₆-C₃₀)aryl(C₁-C₄)alkyl, allyl,(C₁-C₄)alkoxy(C₁-C₄)alkyl, (C₄-C₃₀)cyclo(C₁-C₁₂)-alkyl,(C₁-C₄)alkylcarbonyl, (C₁-C₄)alkyl-carboxy(C₁-C₄)alkyl, haloallyl, C₁-C₄aminoalkyl, (C₁-C₄)(di)alkylamino(C₁-C₄)alkyl, (C₁-C₄)alkyl-sulphonyl,(C₁-C₄)alkoxycarbonyl; halogen; allyl; hydrogenocarbonyl;trifluoromethyl; nitro; cyano; it being understood that at least one ofthe radicals R or R′ represents a group hydroxyl; nitro; cyano; amino;amino optionally substituted with one or more radicals; two radicals Rcarried by two adjacent carbon atoms or two radicals R′ carried by twoadjacent carbon atoms may form with the aromatic ring carrying thecarbon atoms to which each is attached a fused ring of the naphthalenetype optionally substituted with an aminosulphonyl or(C₁-C₄)alkyl(C₁-C₄)aminosulphonyl group; at least one film-formingpolymer.
 27. Composition according to claim 26, characterized in thatthe direct azo dye corresponds to the following formula (Ia):

in which: R′₁ represents a hydrogen atom, an amino group or a hydroxylgroup; R′₂ represents a hydrogen atom, a halogen atom, a carboxylic acidgroup, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, an allyl group or aC₁-C₄ aminocarbonylalkyl group; R′₃ represents a hydrogen atom, ahydroxyl group or a group of the NR″₁R″₂ type where R″₁ and R″₂represent, independently of each other, a hydrogen atom, a C₁-C₄ alkylgroup, a C₂-C₄ alkenyl group, a C₁-C₄ cyanoalkyl group, a C₁-C₄hydroxyalkyl group, a C₆-C₃₀ aryl group, a (C₆-C₃₀)aryl(C₁-C₄)alkylgroup, an allyl group, a (C₁-C₄)alkoxy(C₁-C₄)alkyl group, a(C₄-C₃₀)cyclo(C₁-C₁₂)alkyl group, a (C₁-C₄)alkyl-carbonyl group, a(C₁-C₄)alkylcarboxy(C₁-C₄)alkyl group or a haloallyl group, a C₁-C₄aminoalkyl group, a (C₁-C₄)(di)alkylamino(C₁-C₄)alkyl group; R′₂ and R′₃may form, with the benzene ring, a fused ring of the naphthalene typeoptionally substituted with a group —SO₂—NHR where R represents ahydrogen atom or an optionally substituted C₁-C₄ alkyl chain; R′₄represents a hydrogen atom, a halogen atom, a hydroxyl group, a C₁-C₄alkyl group, a C₁-C₄ alkoxy group, a (C₁-C₄)alkoxy(C₁-C₄)alkyl group;R′₅ represents a hydrogen atom, a halogen atom, a hydroxyl group, anamino group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a(C₁-C₄)alkylcarbonylamino group, a formylamino group, a(C₁-C₄)alkylsulphonylamino group, a (C₁-C₄)alkoxycarbonylamino group ora CF₃ group; R′₄ and R′₅ may form, with the benzene ring, a fused ringof the naphthalene type; R₅ represents a hydrogen atom, a halogen atom,a carboxylic acid group, a hydroxyl group, an amino group, a cyano groupor a C₁-C₄ alkyl group; R₄ represents a hydrogen atom or a nitro group;R₃ represents a hydrogen atom, a C₁-C₄ alkyl group, a C₁-C₄ alkoxygroup, a (C₄-C₃₀)cyclo(C₁-C₁₂)alkyl group, a C₂-C₄ alkenyl group, aC₁-C₄ alkoxycarbonyl group, a (C₁-C₄)alkylcarbonyl group, a(C₁-C₄)alkoxycarbonyl(C₁-C₄)alkoxycarbonyl group, a(C₁-C₄)alkylcarbonyl(C₁-C₄)alkoxycarbonyl group, an aryl group, an aminogroup, a nitro group, a cyano group or a CF₃ group; R₂ represents ahydrogen atom, a nitro group or a C₁-C₄ alkyl group; R₁ represents ahydrogen atom, a halogen atom, a hydroxyl group, a nitro group or acyano group; it being understood that at least one of the radicals R′₁to R′₅ and R₁ to R₅ represents a group hydroxyl; nitro; cyano; amino;amino optionally substituted with one or more radicals.
 28. Compositionaccording to either of claims 26 and 27, characterized in that itcomprises at least one plasticizer.
 29. Composition according to any oneof claims 26 to 28, characterized in that it is in the form of a film.30. Composition according to any one of claims 26 to 29, characterizedin that the film has a thickness of between 0.01 mm and 2 mm, preferably0.02 mm and 0.2 mm.
 31. Method for preparing a composition according toany one of claims 26 to 30, characterized in that a compositioncomprising a mixture comprising at least one direct azo dye, at leastone film-forming polymer and at least one solvent is applied to asupport, and then the said solvent is evaporated.
 32. Method accordingto the preceding claim, characterized in that the composition comprisesfrom 0.0001 to 60% of direct azo dye.
 33. Method according to either ofclaims 31 and 32, characterized in that the composition comprises from0.01 to 80% by weight of film-forming polymer.
 34. Method according toany one of claims 31 to 33, characterized in that the compositioncomprises from 5 to 99.9% by weight of solvent.